Dye composition comprising a para-phenylenediamine oxidation base and a heterocyclic oxidation base

ABSTRACT

The present invention relates to a composition for dyeing keratin fibres, in particular keratin fibres such as the hair, comprising: a) at least one oxidation base 3-(2,5-diaminophenyl)-1-propanol acid salts thereof or solvates thereof such as hydrates; b) at least one heterocyclic oxidation base; c) at least one coupler; d) optionally at least one fatty substance; e) optionally at least one basifying agent; and f) optionally at least one chemical oxidizing agent. The invention also relates to a process for dyeing keratin fibres such as the hair using the composition of the invention, and to a multi-compartment device for using the composition of the invention.

The present invention relates to a composition for dyeing keratin fibresusing a specific para-phenylenediamine oxidation base and a heterocyclicoxidation base.

Many people have sought for a long time to modify the colour of theirhair and in particular to hide their grey hair.

One of the dyeing methods is “permanent” or oxidation dyeing, which usesdye compositions containing oxidation dye precursors, generally known asoxidation bases.

These oxidation bases are colourless or weakly coloured compounds,which, when combined with oxidizing products, may give rise to colouredcompounds via a process of oxidative condensation.

It is also known that the shades obtained with these oxidation bases maybe varied by combining them with couplers or colouring modifiers, thelatter being chosen especially from aromatic meta-diamines,meta-aminophenols, meta-diphenols and certain heterocyclic compoundssuch as indole compounds. The variety of the molecules used as oxidationbases and couplers allows a wide range of colours to be obtained.

Permanent dyeing processes thus consist in using, with the compositioncontaining the dye precursors, an aqueous composition comprising atleast one oxidizing agent, under alkaline pH conditions in the vastmajority of cases. The role of this oxidizing agent is to at leastpartly degrade the melanin of the hair, which, depending on the natureof the oxidizing agent present, leads to more or less pronouncedlightening of the fibres. The oxidizing agent used is generally hydrogenperoxide.

The basifying agent makes it possible to adjust the pH of thecomposition to an alkaline pH to enable activation of the oxidizingagent. In addition, this basifying agent causes swelling of the keratinfibre, with raising of the scales, which promotes the penetration of theoxidizing agent, and also of the dyes, if they are present, essentiallyoxidation dyes, into the fibre, and thus increases the efficacy of thedyeing or lightening reaction.

In the long term, the use of an oxidizing agent and an alkaline agentmay lead to degradation of the keratin fibres and also to inconvenienceat the time of use; in particular, ammonia may give rise toinconvenience to the user due to its strong characteristic odour.

Moreover, not only may the user be inconvenienced by the odour, but hemay also be confronted with greater risks of intolerance, for instanceirritation of the scalp, which is especially reflected by stinging.

It is also important to obtain intense colouring, which is resistant toexternal factors such as light, shampoos and sweat, and which is asuniform as possible along the entire fibre, irrespective of the level ofdamage of the keratin fibre.

Oxidation bases of the para-phenylenediamine type are commonly used inthe field of hair dyeing. It is known practice, for example, to use3-(2,5-diaminophenyl)-1-propanol (or2-γ-hydroxypropyl-para-phenylenediamine) in oxidation dyeing, especiallyin document WO 80/00214. However, the dye compositions obtained usingthis oxidation base are not always satisfactory especially for ensuringsuitable coverage of grey hair with an acceptable colouring selectivitybetween the root and the end and/or sufficient fastness with respect toexternal attacking factors such as light, shampoos, bad weather, etc.

One of the objects of the present invention is to propose compositionsfor dyeing human keratin fibres such as the hair, which have superiordyeing properties relative to the existing compositions.

In particular, the composition according to the invention in thepresence of a chemical oxidizing agent must make it possible to obtaincolours that are satisfactory, especially in terms of power, but alsowith sufficient uniformity of the colour from the end to the root of thehair, which makes it possible to avoid a “root” effect of the colouring.Finally, it is also possible to obtain colourings that are very stabletowards external agents.

Furthermore, the invention makes it possible to achieve substantialdegrees of lightening while at the same time colouring, and does sowithout using oxidizing agents such as persalts or increasing the amountof chemical oxidizing agent or of basifying agent.

Moreover, the composition of the invention makes it possible to obtainformulations that are less malodorous during their application to thehair or during their preparation.

These aims and others are achieved by the present invention, one subjectof which is thus a composition for dyeing keratin fibres, in particularhuman keratin fibres such as the hair, comprising:

-   -   a) at least one oxidation base 3-(2,5-diaminophenyl)-1-propanol        and/or acid salts thereof and/or solvates thereof such as        hydrates;    -   b) at least one heterocyclic oxidation base as defined in claim        1;    -   c) at least one coupler;    -   d) optionally at least one fatty substance, which is preferably        liquid and non-silicone-based;    -   e) optionally at least one basifying agent; and    -   f) optionally at least one chemical oxidizing agent.

A subject of the invention is also a process for dyeing keratin fibressuch as the hair using the composition of the invention, and amulti-compartment device for using the composition of the invention.

Furthermore, the processes according to the invention use formulationsthat are less malodorous during their application to the hair or duringtheir preparation.

Other characteristics and advantages of the invention will emerge moreclearly on reading the description and the examples that follow.

In the text hereinbelow, and unless otherwise indicated, the limits of arange of values are included within that range. The expression “at leastone” is equivalent to the expression “one or more”.

d) Fatty Substances

As has already been mentioned, the composition of the invention maycomprise one or more fatty substances.

The term “fatty substance” means an organic compound that is insolublein water at ordinary temperature (25° C.) and at atmospheric pressure(760 mmHg) (solubility of less than 5%, preferably less than 1% and evenmore preferentially less than 0.1%). They bear in their structure atleast one hydrocarbon-based chain comprising at least 6 carbon atoms ora sequence of at least two siloxane groups. In addition, the fattysubstances are generally soluble in organic solvents under the sametemperature and pressure conditions, for instance chloroform,dichloromethane, carbon tetrachloride, ethanol, benzene, toluene,tetrahydrofuran (THF), liquid petroleum jelly ordecamethylcyclopentasiloxane.

Preferably, the fatty substances of use in the invention do not containany salified or unsalified carboxylic acid groups (—C(O)OH or —C(O)O⁻).The fatty substances of the invention are neither polyoxyalkylenated norpolyglycerolated.

Preferably, the fatty substances used in the composition according tothe invention are non-silicone oils.

The term “oil” means a “fatty substance” that is liquid at roomtemperature (25° C.) and at atmospheric pressure (760 mmHg).

The term “non-silicone oil” means an oil not containing any siliconatoms (Si) and the term “silicone oil” means an oil containing at leastone silicon atom.

More particularly, the fatty substances are chosen from C₆-C₁₆hydrocarbons, hydrocarbons containing more than 16 carbon atoms,non-silicone oils of animal origin, plant oils of triglyceride type,synthetic triglycerides, fluoro oils, fatty alcohols, esters of fattyacids and/or of fatty alcohols other than triglycerides, and plantwaxes, non-silicone waxes and silicones.

It is recalled that, for the purposes of the invention, the fattyalcohols, fatty esters and fatty acids more particularly contain one ormore linear or branched, saturated or unsaturated hydrocarbon-basedgroups comprising 6 to 30 carbon atoms, which are optionallysubstituted, in particular, with one or more (in particular 1 to 4)hydroxyl groups. If they are unsaturated, these compounds may compriseone to three conjugated or unconjugated carbon-carbon double bonds.

As regards the C₆-C₁₆ hydrocarbons, they are linear, branched oroptionally cyclic, and are preferably alkanes. Examples that may bementioned include hexane, dodecane and isoparaffins such asisohexadecane and isodecane.

A hydrocarbon-based oil of animal origin that may be mentioned isperhydrosqualene.

The triglyceride oils of plant or synthetic origin are preferably chosenfrom liquid fatty acid triglycerides containing from 6 to 30 carbonatoms, for instance heptanoic or octanoic acid triglycerides, oralternatively, for example, sunflower oil, corn oil, soybean oil,pumpkin oil, grapeseed oil, sesame seed oil, hazelnut oil, apricot oil,macadamia oil, arara oil, castor oil, avocado oil, caprylic/capric acidtriglycerides, for instance those sold by the company StearineriesDubois or those sold under the names Miglyol® 810, 812 and 818 by thecompany Dynamit Nobel, jojoba oil and shea butter oil.

The linear or branched hydrocarbons of mineral or synthetic origincontaining more than 16 carbon atoms are preferably chosen from liquidparaffins, petroleum jelly, liquid petroleum jelly, polydecenes andhydrogenated polyisobutene such as Parleam®.

The fluoro oils may be chosen from perfluoromethylcyclopentane andperfluoro-1,3-dimethylcyclohexane, sold under the names Flutec® PC1 andFlutec® PC3 by the company BNFL Fluorochemicals;perfluoro-1,2-dimethylcyclobutane; perfluoroalkanes such asdodecafluoropentane and tetradecafluorohexane, sold under the names PF5050® and PF 5060® by the company 3M, or alternativelybromoperfluorooctyl sold under the name Foralkyl® by the companyAtochem; nonafluoromethoxybutane and nonafluoroethoxyisobutane;perfluoromorpholine derivatives such as 4-trifluoromethylperfluoromorpholine sold under the name PF 5052® by the company 3M.

The fatty alcohols that may be used in the composition according to theinvention are saturated or unsaturated, and linear or branched, andcomprise from 6 to 30 carbon atoms and more particularly from 8 to 30carbon atoms. Mention may be made, for example, of cetyl alcohol,stearyl alcohol and a mixture thereof (cetearyl alcohol),octyldodecanol, 2-butyloctanol, 2-hexyldecanol, 2-undecylpentadecanol,oleyl alcohol or linoleyl alcohol.

The wax(es) that may be used in the composition according to theinvention are chosen especially from carnauba wax, candelilla wax,esparto grass wax, paraffin wax, ozokerite, plant waxes, for instanceolive wax, rice wax, hydrogenated jojoba wax or the absolute waxes offlowers such as the essential wax of blackcurrant blossom sold by thecompany Bertin (France), animal waxes, for instance beeswaxes, ormodified beeswaxes (cerabellina); other waxes or waxy starting materialsthat may be used according to the invention are especially marine waxessuch as the product sold by the company Sophim under the reference M82,and polyethylene waxes or polyolefin waxes in general.

As regards the fatty acid and/or fatty alcohol esters, which areadvantageously different from the triglycerides mentioned above, mentionmay be made in particular of esters of saturated or unsaturated, linearor branched C₁-C₂₆ aliphatic mono- or polyacids and of saturated orunsaturated, linear or branched C₁-C₂₆ aliphatic mono- or polyalcohols,the total carbon number of the esters more particularly being greaterthan or equal to 10.

Among the monoesters, mention may be made of dihydroabietyl behenate;octyldodecyl behenate; isocetyl behenate; cetyl lactate; C₁₂-C₁₅ alkyllactate; isostearyl lactate; lauryl lactate; linoleyl lactate; oleyllactate; (iso)stearyl octanoate; isocetyl octanoate; octyl octanoate;cetyl octanoate; decyl oleate; isocetyl isostearate; isocetyl laurate;isocetyl stearate; isodecyl octanoate; isodecyl oleate; isononylisononanoate; isostearyl palmitate; methylacetyl ricinoleate; myristylstearate; octyl isononanoate; 2-ethylhexyl isononanoate; octylpalmitate; octyl pelargonate; octyl stearate; octyldodecyl erucate;oleyl erucate; ethyl and isopropyl palmitates, 2-ethylhexyl palmitate,2-octyldecyl palmitate, alkyl myristates such as isopropyl, butyl,cetyl, 2-octyldodecyl, myristyl or stearyl myristate, hexyl stearate,butyl stearate, isobutyl stearate; dioctyl malate, hexyl laurate,2-hexyldecyl laurate.

Still within the context of this variant, esters of C₄-C₂₂ dicarboxylicor tricarboxylic acids and of C₁-C₂₂ alcohols and esters of mono-, di-or tricarboxylic acids and of C₂-C₂₆ di-, tri-, tetra- or pentahydroxyalcohols may also be used.

Mention may be made in particular of: diethyl sebacate; diisopropylsebacate; diisopropyl adipate; di-n-propyl adipate; dioctyl adipate;diisostearyl adipate; dioctyl maleate; glyceryl undecylenate;octyldodecyl stearoyl stearate; pentaerythrityl monoricinoleate;pentaerythrityl tetraisononanoate; pentaerythrityl tetrapelargonate;pentaerythrityl tetraisostearate; pentaerythrityl tetraoctanoate;propylene glycol dicaprylate; propylene glycol dicaprate, tridecylerucate; triisopropyl citrate; triisostearyl citrate; glyceryltrilactate; glyceryl trioctanoate; trioctyldodecyl citrate; trioleylcitrate, propylene glycol dioctanoate; neopentyl glycol diheptanoate;diethylene glycol diisononanoate; and polyethylene glycol distearates.

Among the esters mentioned above, it is preferred to use ethyl,isopropyl, myristyl, cetyl or stearyl palmitate, 2-ethylhexyl palmitate,2-octyldecyl palmitate, alkyl myristates such as isopropyl, butyl, cetylor 2-octyldodecyl myristate, hexyl stearate, butyl stearate, isobutylstearate; dioctyl malate, hexyl laurate, 2-hexyldecyl laurate, isononylisononanoate or cetyl octanoate.

The composition may also comprise, as fatty ester, sugar esters anddiesters of C₆-C₃₀ and preferably C₁₂-C₂₂ fatty acids. It is recalledthat the term “sugar” means oxygen-bearing hydrocarbon-based compoundsbearing several alcohol functions, with or without aldehyde or ketonefunctions, and which comprise at least 4 carbon atoms. These sugars maybe monosaccharides, oligosaccharides or polysaccharides.

Examples of suitable sugars that may be mentioned include sucrose (orsaccharose), glucose, galactose, ribose, fucose, maltose, fructose,mannose, arabinose, xylose and lactose, and derivatives thereof, inparticular alkyl derivatives, such as methyl derivatives, for instancemethylglucose.

The sugar esters of fatty acids may be chosen in particular from thegroup comprising the esters or mixtures of esters of sugars describedpreviously and of linear or branched, saturated or unsaturated C₆-C₃₀and preferably C₁₂-C₂₂ fatty acids. If they are unsaturated, thesecompounds may comprise one to three conjugated or unconjugatedcarbon-carbon double bonds.

The esters according to this alternative form can also be chosen frommono-, di-, tri- and tetraesters and polyesters, and mixtures thereof.

These esters may be, for example, oleates, laurates, palmitates,myristates, behenates, cocoates, stearates, linoleates, linolenates,caprates or arachidonates, or mixtures thereof such as, in particular,oleate/palmitate, oleate/stearate or palmitate/stearate mixed esters.

More particularly, use is made of mono- and diesters and in particularmono- or di-oleate, -stearate, -behenate, -oleate/palmitate, -linoleate,-linolenate or -oleate/stearate of sucrose, glucose or methylglucose. Anexample that may be mentioned is the product sold under the nameGlucate® DO by the company Amerchol, which is a methylglucose dioleate.

Examples of sugar esters or mixtures of sugar esters of fatty acids thatmay also be mentioned include:

-   -   the products sold under the names F160, F140, F110, F90, F70 and        SL40 by the company Crodesta, respectively denoting sucrose        palmitostearates formed from 73% monoester and 27% diester and        triester, from 61% monoester and 39% diester, triester and        tetraester, from 52% monoester and 48% diester, triester and        tetraester, from 45% monoester and 55% diester, triester and        tetraester, from 39% monoester and 61% diester, triester and        tetraester, and sucrose monolaurate;    -   the products sold under the name Ryoto Sugar Esters, for example        referenced B370 and corresponding to sucrose behenate formed        from 20% monoester and 80% di-triester-polyester;    -   the sucrose monopalmitostearate-dipalmitostearate sold by the        company Goldschmidt under the name Tegosoft® PSE.

The silicones that may be used in accordance with the invention may bein the form of oils, waxes, resins or gums.

Preferably, the silicone is chosen from polydialkylsiloxanes, inparticular polydimethylsiloxanes (PDMSs), and organomodifiedpolysiloxanes comprising at least one functional group chosen from aminogroups, aryl groups and alkoxy groups.

Organopolysiloxanes are defined in greater detail in Walter Noll'sChemistry and Technology of Silicones (1968), Academic Press. They maybe volatile or non-volatile.

These silicones are more particularly chosen from polydialkylsiloxanes,among which mention may be made mainly of polydimethylsiloxanes bearingtrimethylsilyl end groups. The viscosity of the silicones is measured at25° C. according to ASTM Standard 445 Appendix C.

Among these polydialkylsiloxanes, mention may be made, in a nonlimitingmanner, of the following commercial products:

-   -   the Silbione® oils of the 47 and 70 047 series or the Mirasil®        oils sold by Rhodia, for instance the oil 70 047 V 500 000;    -   the oils of the Mirasil® series sold by the company Rhodia;    -   the oils of the 200 series from the company Dow Corning, such as        DC200 with—a viscosity of 60 000 mm²/s;    -   the Viscasil® oils from General Electric and certain oils of the        SF series (SF 96, SF 18) from General Electric.

Mention may also be made of polydimethylsiloxanes having dimethylsilanolend groups known under the name dimethiconol (CTFA), such as the oils ofthe 48 series from the company Rhodia.

In this category of polydialkylsiloxanes, mention may also be made ofthe products sold under the names Abil Wax® 9800 and 9801 by the companyGoldschmidt, which are poly(C₁-C₂₀)dialkylsiloxanes.

The organomodified silicones that may be used in accordance with theinvention are silicones as defined previously and comprising in theirstructure one or more organofunctional groups attached via ahydrocarbon-based group.

The organomodified silicones may be polydiarylsiloxanes, in particularpolydiphenylsiloxanes, and polyalkylarylsiloxanes functionalized withthe organofunctional groups mentioned previously.

The polyalkylarylsiloxanes are particularly chosen from linear and/orbranched polydimethyl/methylphenylsiloxanes andpolydimethyl/diphenylsiloxanes with a viscosity ranging from 1×10⁻⁵ to5×10⁻² m²/s at 25° C.

Among these polyalkylarylsiloxanes, examples that may be mentionedinclude the products sold under the following names:

-   -   the Silbione® oils of the 70 641 series from Rhodia;    -   oils of the Rhodorsil® 70 633 and 763 series from Rhodia;    -   the oil Dow Corning 556 Cosmetic Grade Fluid from Dow Corning;    -   the silicones of the PK series from Bayer, such as the product        PK20;    -   the silicones of the PN and PH series from Bayer, such as the        products PN1000 and PH1000;    -   certain oils of the SF series from General Electric, such as SF        1023, SF 1154, SF 1250 and SF 1265.

Among the organomodified silicones, mention may also be made ofpolyorganosiloxanes comprising:

-   -   substituted or unsubstituted amino groups, such as the products        sold under the names GP 4 Silicone Fluid and GP 7100 by the        company Genesee or the products sold under the names Q2 8220 and        Dow Corning 929 or 939 by the company Dow Corning. The        substituted amino groups are, in particular, C₁-C₄ aminoalkyl        groups;    -   alkoxy groups such as the product sold under the name Silicone        Copolymer F-755 by SWS Silicones, and Abil Wax® 2428, 2434 and        2440 by the company Goldschmidt.

Preferably, the fatty substances according to the invention arenon-silicone.

The fatty substances are advantageously chosen from C₆-C₁₆ hydrocarbons,hydrocarbons containing more than 16 carbon atoms, triglycerides, fattyalcohols, esters of fatty acids and/or of fatty alcohols other thantriglycerides, or mixtures thereof, which are preferably liquid.

Preferably, the fatty substance(s) are chosen from liquid petroleumjelly, polydecenes, liquid fatty alcohols, liquid esters of fatty acidsand/or of fatty alcohols, or mixtures thereof.

Even more preferentially, the fatty substances are chosen from liquidpetroleum jelly and octyldodecanol.

According to a particular embodiment, the composition contains at leastone fatty substance. When they are present, the content of fattysubstances is preferably at least 10% by weight relative to the totalweight of the composition.

According to this particular embodiment, the composition according tothe invention comprises at least 10% by weight of non-silicone fattysubstances, in particular non-silicone oils, relative to the totalweight of the composition of the invention. More particularly, thecomposition according to the invention comprises at least 25% by weightof fatty substances, which are preferably non-silicone, in particularnon-silicone oils, relative to the total weight of the composition.

The composition according to the invention more particularly has a fattysubstance content ranging from 15% to 80% by weight, preferably from 25%to 75% by weight, better still from 30% to 70% by weight and even moreadvantageously from 30% to 60% by weight relative to the weight of thecomposition.

According to a particular embodiment, when the composition contains theoxidizing agent and the basifying agent, then the composition accordingto the invention preferably contains more than 25% of fatty substances.According to this variant, the composition preferably contains more than30% of fatty substances.

b) Heterocyclic Oxidation Bases

According to the invention, the term “heterocyclic base” means anoxidation base comprising a 5-, 6-, 7- or 8-membered aromatic ornon-aromatic ring and from 1 to 3 heteroatoms chosen from nitrogen,sulfur and oxygen atoms. These heterocycles may be fused to otherheterocycles or to a phenyl group. They may be substituted with ahalogen atom; a (C₁-C₄)alkyl radical; a (C₁-C₄)alkoxy radical; ahydroxyl radical; an amino radical; a (C₁-C₄)alkylamino radical;di(C₁-C₄)alkylamino in which the two alkyl groups may, together with thenitrogen atom to which they are attached, form a ring that may beinterrupted with one or more nitrogen, oxygen or sulfur atoms. Theseheterocycles may also be quaternized with a (C₁-C₄)alkyl radical. Thealkyl or alkoxy radicals described above may optionally be substituted,preferably with one or more hydroxyl or amino groups.

The term “cationic heterocycle” means a heterocycle as describedpreviously containing one or more cationic radicals of the quaternaryammonium type.

Examples of cationic radicals that may be mentioned include radicals ofthe type —N⁺R₁₇R₁₈R₁₉, for example trimethylammonium, triethylammonium,dimethylethylammonium, diethylmethylammonium, diisopropylmethylammonium,diethylpropylammonium, β-hydroxyethyldiethylammonium,di(β-hydroxyethyl)-methylammonium and tri(β-hydroxyethyl)ammoniumradicals. Examples of cationic heterocycles that may be mentionedinclude imidazolium, pyridinium, piperazinium, pyrrolidinium,morpholinium, pyrimidinium, thiazolium, benzimidazolium,benzothiazolium, oxazolium, benzotriazolium, pyrazolium, triazolium andbenzoxazolium heterocycles.

As heterocyclic oxidation bases that are useful in the presentinvention, mention may be made of pyridines, pyrimidines,aminopyrazolones, aminopyrrolidines, aminopyrazolines andaminoindazoles, and derivatives thereof.

The heterocyclic bases are more particularly chosen from pyridinederivatives, pyrimidine derivatives and pyrazolone derivatives and theaddition salts thereof or solvates thereof.

Among the pyridine derivatives, mention may be made of the compoundsdescribed, for example, in patents GB 1 026 978 and GB 1 153 196, forinstance 2,5-diaminopyridine, 2-(4-methoxyphenyl)amino-3-aminopyridineand 3,4-diaminopyridine, and the addition salts thereof or solvatesthereof.

Other pyridine oxidation bases that are useful according to theinvention are the 3-aminopyrazolo[1,5-a]pyridine oxidation bases or theaddition salts thereof described, for example, in patent application FR2 801 308. Examples that may be mentioned includepyrazolo[1,5-a]pyrid-3-ylamine,2-acetylaminopyrazolo[1,5-a]pyrid-3-ylamine,2-(morpholin-4-yl)pyrazolo[1,5-a]pyrid-3-ylamine,3-aminopyrazolo[1,5-a]pyridine-2-carboxylic acid,2-methoxypyrazolo[1,5-a]pyrid-3-ylamino,(3-aminopyrazolo[1,5-a]pyrid-7-yl)methanol,2-(3-aminopyrazolo[1,5-a]pyrid-5-yl)ethanol,2-(3-aminopyrazolo[1,5-a]pyrid-7-yl)ethanol,(3-aminopyrazolo[1,5-a]pyrid-2-yl)methanol,3,6-diaminopyrazolo[1,5-a]pyridine, 3,4-diaminopyrazolo[1,5-a]pyridine,pyrazolo[1,5-a]pyridine-3,7-diamine,7-(morpholin-4-yl)pyrazolo[1,5-a]pyrid-3-ylamine,pyrazolo[1,5-a]pyridine-3,5-diamine,5-(morpholin-4-yl)pyrazolo[1,5-a]pyrid-3-ylamine,2-[(3-aminopyrazolo[1,5-a]pyrid-5-yl)(2-hydroxyethyl)amino]ethanol,2-[(3-aminopyrazolo[1,5-a]pyrid-7-yl)(2-hydroxyethyl)amino]ethanol,3-aminopyrazolo[1,5-a]pyridin-5-ol, 3-aminopyrazolo[1,5-a]pyridin-4-ol,3-aminopyrazolo[1,5-a]pyridin-6-ol, 3-aminopyrazolo[1,5-a]pyridin-7-ol,2-[(3-aminopyrazolo[1,5-a]pyrid-2-yl)oxy]ethanol and also the additionsalts thereof or solvates thereof.

Among the pyrimidine derivatives, mention may be made of the compoundsdescribed, for example, in patents DE 2359399, JP 88169571, JP 05-63124and EP 0 770 375 or patent application WO 96/15765, such as2,4,5,6-tetraaminopyrimidine, 4-hydroxy-2,5,6-triaminopyrimidine,2-hydroxy-4,5,6-triaminopyrimidine, 2,4-dihydroxy-5,6-diaminopyrimidine,2,5,6-triaminopyrimidine and the addition salts thereof, and thetautomeric forms thereof, when a tautomeric equilibrium exists.

Pyrazole derivatives that may also be mentioned includediamino-N,N-dihydropyrazolopyrazolones and especially those described inpatent application FR-A-2 886 136, such as the following compounds andthe addition salts thereof:2,3-diamino-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-one,2-amino-3-ethylamino-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-one,2-amino-3-isopropylamino-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-one,2-amino-3-(pyrrolidin-1-yl)-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-one,4,5-diamino-1,2-dimethyl-1,2-dihydropyrazol-3-one,4,5-diamino-1,2-diethyl-1,2-dihydropyrazol-3-one,4,5-diamino-1,2-bis(2-hydroxyethyl)-1,2-dihydropyrazol-3-one,2-amino-3-(2-hydroxyethyl)amino-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-one,2-amino-3-dimethylamino-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-one,2,3-diamino-5,6,7,8-tetrahydro-1H,6H-pyridazino[1,2-a]pyrazol-1-one,4-amino-1,2-diethyl-5-(pyrrolidin-1-yl)-1,2-dihydropyrazol-3-one,4-amino-5-(3-dimethylaminopyrrolidin-1-yl)-1,2-diethyl-1,2-dihydropyrazol-3-oneor 2,3-diamino-6-hydroxy-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-one.

According to a particularly preferred embodiment, the heterocyclicoxidation base(s) are chosen from the compounds of formula (I), theaddition salts thereof and solvates thereof:

in which R₁ represents an amino group, a C₁ to C₄ alkyl group,optionally substituted with one or more hydroxyl or amino groups, a C₁to C₄ alkoxy group, optionally substituted with one or more hydroxyl oramino groups.

(i) the compounds of formula (II) or (Ill), the addition salts thereofand solvates thereof:

in which R₂ represents an amino group, a C₁ to C₄ alkyl group,optionally substituted with one or more hydroxyl or amino groups, a C₁to C₄ alkoxy group, optionally substituted with one or more hydroxyl oramino groups; and Z, represents a covalent bond, a radical—NR′₆(CH₂)_(q)— or a radical —O(CH₂)_(p)— with R′₆ representing ahydrogen atom, a C₁-C₆ alkyl radical optionally substituted with one ormore hydroxyl groups, p denoting an integer ranging from 0 to 6, qdenoting an integer ranging from 0 to 6 and R′₁ is a cationic radical;and

the radicals R′₃, R′₄ and R′₅ may independently be a hydrogen atom or aC₁-C₄ alkyl radical which may be substituted. Examples that may bementioned include methyl, ethyl, hydroxyethyl, aminoethyl, propyl andbutyl radicals. According to a particular embodiment, R′₃, R′₄ and R′₅independently represent a hydrogen atom or a C₁-C₄ alkyl radical.

R′₄ and R′₅ may together form a partially saturated or unsaturated 5- or8-membered ring, especially an optionally substituted cyclopentene orcyclohexene.

As cationic groups, mention may be made for R′₁ of a cationicheterocycle or a heterocycle substituted with a cationic radical.Examples that may be mentioned include imidazoles substituted with aquaternary ammonium radical or imidazoliums, piperazines substitutedwith a quaternary ammonium radical or piperaziniums, pyrrolidinessubstituted with a quaternary ammonium radical or pyrrolidiniums, anddiazepanes substituted with a quaternary ammonium radical ordiazepaniums. R′₁ may also be chosen from trialkylammonium,tri(hydroxyalkyl)ammonium, hydroxyalkyl-dialkyl-ammonium anddi(hydroxyalkyl)alkylammonium cationic radicals.

Preferably, in the compounds of formula (I), R₁ represents an aminogroup.

Preferably, in the compounds of formula (II), R₂ represents a C₁ to C₄alkoxy group, optionally substituted with one or more hydroxyl groups,and preferentially represents a hydroxyethoxy group.

Among the compounds of formula (I) it will be preferred to use2,3-diamino-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-one, an additionsalt thereof or a solvate thereof.

Among the compounds of formula (II) it will be preferred to use2-[(3-aminopyrazolo[1,5-a]pyrid-2-yl)oxy]ethanol, an addition saltthereof or a solvate thereof.

For the vast majority, the 3-aminopyrazolo[1,5-a]pyridines of formulae(II) and (III) are known compounds and are described especially inpatent U.S. Pat. No. 5,457,200. These compounds may be preparedaccording to synthetic methods that are well known in the literature andas described, for example, in patent U.S. Pat. No. 5,457,200.

As examples of derivatives of formula (III), mention may be made of thefollowing compounds:

The radical X represents an ion or a group of ions for ensuring theelectronegativity of the derivative of formula (III).

As heterocyclic bases that are useful for the invention, use willpreferentially be made of2,3-diamino-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-one and/or2-[(3-aminopyrazolo[1,5-a]pyrid-2-yl)oxy]ethanol and/or a salt orsolvate thereof, and2,3-diamino-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-one and/or a saltor solvate thereof.

As cationic oxidation bases of formula (III), the following bases aremost particularly preferred:

The salts of the heterocyclic oxidation bases that may be used accordingto the invention may be chosen from the hydrochlorides, hydrobromides,sulfates, citrates, succinates, tartrates, lactates, tosylates,methanesulfonates, benzenesulfonates, phosphates and acetates.

The composition of the invention may contain one or more heterocyclicbases described above.

In the composition of the invention, the heterocyclic oxidation base(s)are present in an amount generally between 0.0001% and 20% by weightrelative to the total weight of the composition, preferably from 0.005%to 10% by weight and more particularly from 0.01% to 10% by weightrelative to the total weight of the composition.

a) 3-(2,5-Diaminophenyl)-1-propanol oxidation bases:

The composition of the invention comprises c) one or more oxidationbases chosen from 3-(2,5-diaminophenyl)-1-propanol (or2-γ-hydroxypropyl-para-phenylenediamine) having the following formula,the acid salts thereof or the solvates thereof such as hydrates:

The oxidation base(s) chosen from (2,5-diaminophenyl)propanol, the acidsalts thereof or the solvates thereof such as hydrates, according to theinvention, may be present in the composition of the invention in anamount ranging from 0.0001% to 20% by weight relative to the totalweight of the composition, preferably from 0.005% to 10% by weight andmore particularly from 0.01% to 10% by weight relative to the totalweight of the composition.

The acid salts that may be used according to the invention may be chosenfrom hydrochlorides, hydrobromides, sulfates, citrates, succinates,tartrates, lactates, tosylates, benzenesulfonates, phosphates andacetates.

Additional Oxidation Bases

The composition according to the invention may comprise one or moreadditional oxidation bases other than 3-(2,5-diaminophenyl)-1-propanoland the heterocyclic oxidation bases and the acid salts thereof or thesolvates thereof such as hydrates.

As examples of additional benzene-based oxidation bases, mention may bemade of para-phenylenediamines other than3-(2,5-diaminophenyl)-1-propanol, bis(phenyl)alkylenediamines,para-aminophenols, ortho-aminophenols, and the addition salts thereof orsolvates thereof.

Among the para-phenylenediamines, examples that may be mentioned includepara-phenylenediamine, para-tolylenediamine,2-chloro-para-phenylenediamine, 2,3-dimethyl-para-phenylenediamine,2,6-dimethyl-para-phenylenediamine, 2,6-diethyl-para-phenylenediamine,2,5-dimethyl-para-phenylenediamine, N,N-dimethyl-para-phenylenediamine,N,N-diethyl-para-phenylenediamine, N,N-dipropyl-para-phenylenediamine,4-amino-N,N-diethyl-3-methylaniline,N,N-bis(β-hydroxyethyl)-para-phenylenediamine,4-N,N-bis(β-hydroxyethyl)amino-2-methylaniline,4-N,N-bis(β-hydroxyethyl)amino-2-chloroaniline,2-fluoro-para-phenylenediamine, 2-isopropyl-para-phenylenediamine,N-(β-hydroxypropyl)-para-phenylenediamine,2-hydroxymethyl-para-phenylenediamine,N,N-dimethyl-3-methyl-para-phenylenediamine,N-ethyl-N-(β-hydroxyethyl)-para-phenylenediamine,N-(β,γ-dihydroxypropyl)-para-phenylenediamine,N-(4′-aminophenyl)-para-phenylenediamine,N-phenyl-para-phenylenediamine,2-β-hydroxyethyloxy-para-phenylenediamine,2-β-acetylaminoethyloxy-para-phenylenediamine,N-(β-methoxyethyl)-para-phenylenediamine, 4-aminophenylpyrrolidine,2-thienyl-para-phenylenediamine, 2-β-hydroxyethylamino-5-aminotoluene,3-hydroxy-1-(4′-aminophenyl)pyrrolidine, and the addition salts thereofwith an acid, or the solvates thereof.

Among the para-phenylenediamines mentioned above, para-phenylenediamineor PPD, para-tolylenediamine or PTD, 2-isopropyl-para-phenylenediamine,2-β-hydroxyethyloxy-para-phenylenediamine,2,6-dimethyl-para-phenylenediamine, 2,6-diethyl-para-phenylenediamine,2,3-dimethyl-para-phenylenediamine,N,N-bis(3-hydroxyethyl)-para-phenylenediamine,2-chloro-para-phenylenediamine and2-β-acetylaminoethyloxy-para-phenylenediamine, and the addition saltsthereof with an acid, or the solvates thereof, are particularlypreferred.

Among the bis(phenyl)alkylenediamines, examples that may be mentionedincludeN,N′-bis(β-hydroxyethyl)-N,N′-bis(4′-aminophenyl)-1,3-diaminopropanol,N,N′-bis(β-hydroxyethyl)-N,N′-bis(4′-aminophenyl)ethylenediamine,N,N′-bis(4-aminophenyl)tetramethylenediamine,N,N′-bis(β-hydroxyethyl)-N,N′-bis(4-aminophenyl)tetramethylenediamine,N,N′-bis(4-methylaminophenyl)tetramethylenediamine,N,N′-bis(ethyl)-N,N′-bis(4′-amino-3′-methylphenyl)ethylenediamine and1,8-bis(2,5-diaminophenoxy)-3,6-dioxaoctane, and the addition saltsthereof, or the solvates thereof.

Among the para-aminophenols that may be mentioned, for example, arepara-aminophenol, 4-amino-3-methylphenol, 4-amino-3-fluorophenol,4-amino-3-chlorophenol, 4-amino-3-hydroxymethylphenol,4-amino-2-methylphenol, 4-amino-2-hydroxymethylphenol,4-amino-2-methoxymethylphenol, 4-amino-2-aminomethylphenol,4-amino-2-(β-hydroxyethylaminomethyl)phenol and 4-amino-2-fluorophenol,and the addition salts thereof with an acid, or the solvates thereof.

Among the ortho-aminophenols, examples that may be mentioned include2-aminophenol, 2-amino-5-methylphenol, 2-amino-6-methylphenol,5-acetamido-2-aminophenol and the addition salts thereof, or thesolvates thereof.

The additional oxidation base(s) according to the invention eachadvantageously represent from 0.0001% to 10% by weight relative to thetotal weight of the composition, and preferably from 0.005% to 5% byweight relative to the total weight of the composition.

c) Couplers

The composition of the invention comprises at least one coupler. Amongthese couplers, mention may be made especially ofmeta-phenylenediamines, meta-aminophenols, meta-diphenols,naphthalene-based couplers and heterocyclic couplers, and the additionsalts or solvates thereof.

Examples that may be mentioned include 1,3-dihydroxybenzene,1,3-dihydroxy-2-methylbenzene, 4-chloro-1,3-dihydroxybenzene,1-hydroxy-3-aminobenzene, 2,4-diamino-1-(β-hydroxyethyloxy)benzene,1-methyl-2-hydroxy-4-β-hydroxyethylamino benzene,2-methyl-5-aminophenol, 5-amino-6-chloro-2-methylphenol,2-amino-4-(β-hydroxyethylamino)-1-methoxybenzene, 1,3-diaminobenzene,1,3-bis(2,4-diaminophenoxy)propane, 3-ureidoaniline,3-ureido-1-dimethylaminobenzene, sesamol,1-β-hydroxyethylamino-3,4-methylenedioxybenzene, α-naphthol,2-methyl-1-naphthol, 6-hydroxyindole, 4-hydroxyindole,4-hydroxy-N-methylindole, 2-amino-3-hydroxypyridine,6-hydroxybenzomorpholine, 3,5-diamino-2,6-dimethoxypyridine,1-N-(β-hydroxyethyl)amino-3,4-methylenedioxybenzene,2,6-bis(β-hydroxyethylamino)toluene, 6-hydroxyindoline,2,6-dihydroxy-4-methylpyridine, 1-H-3-methylpyrazol-5-one,1-phenyl-3-methylpyrazol-5-one,2,6-dimethylpyrazolo[1,5-b]-1,2,4-triazole,2,6-dimethyl[3,2-c]-1,2,4-triazole and6-methylpyrazolo[1,5-a]benzimidazole, the addition salts thereof with anacid or the solvates thereof, and mixtures thereof.

The coupler(s) each advantageously represent from 0.0001% to 10% byweight relative to the total weight of the composition and preferablyfrom 0.005% to 5% by weight relative to the total weight of thecomposition of the invention.

In general, the addition salts of the oxidation bases and couplers thatmay be used within the context of the invention are especially chosenfrom the addition salts with an acid such as the hydrochlorides,hydrobromides, sulfates, citrates, succinates, tartrates, lactates,tosylates, benzenesulfonates, phosphates and acetates.

Additional Dyes

The composition of the invention may also comprise one or more directdyes. The latter dyes are more particularly chosen from ionic ornonionic species, preferably cationic or nonionic species. These directdyes may be synthetic or of natural origin. When they are present, thedirect dye(s) more particularly represent from 0.0001% to 10% by weightand preferably from 0.005% to 5% by weight relative to the total weightof the composition.

Basifying Agents:

The composition of the invention may also comprise one or more basifyingagents. The basifying agent(s) may be mineral or organic or hybrid.

The mineral basifying agent(s) are preferably chosen from ammonia,alkali metal carbonates or bicarbonates such as sodium or potassiumcarbonates and sodium or potassium bicarbonates, sodium hydroxide orpotassium hydroxide, or mixtures thereof.

The organic basifying agent(s) are preferably chosen from organic amineswith a pK_(b) at 25° C. of less than 12, preferably less than 10 andeven more advantageously less than 6. It should be noted that it is thepK_(b) corresponding to the function of highest basicity. In addition,the organic amines do not comprise any alkyl or alkenyl fatty chaincomprising more than ten carbon atoms.

The organic basifying agent(s) are chosen, for example, fromalkanolamines, oxyethylenated and/or oxypropylenated ethylenediamines,amino acids and the compounds of formula (T) below:

in which formula (T) W is a divalent C₁-C₆ alkylene radical optionallysubstituted with one or more hydroxyl groups or a C₁-C₆ alkyl radical,and/or optionally interrupted with one or more heteroatoms such as O, orNR_(u); R_(x), R_(y), R_(z), R_(t) and R_(u), which may be identical ordifferent, represent a hydrogen atom or a C₁-C₆ alkyl, C₁-C₆hydroxyalkyl or C₁-C₆ aminoalkyl radical.

Examples of amines of formula (T) that may be mentioned include1,3-diaminopropane, 1,3-diamino-2-propanol, spermine and spermidine.

The term “alkanolamine” means an organic amine comprising a primary,secondary or tertiary amine function, and one or more linear or branchedC₁-C₈ alkyl groups bearing one or more hydroxyl radicals.

Organic amines chosen from alkanolamines such as monoalkanolamines,dialkanolamines or trialkanolamines comprising one to three identical ordifferent C₁-C₄ hydroxyalkyl radicals are in particular suitable forperforming the invention.

Among the compounds of this type, mention may be made ofmonoethanolamine (MEA), diethanolamine, triethanolamine,monoisopropanolamine, diisopropanolamine, N-dimethylaminoethanolamine,2-amino-2-methyl-1-propanol, triisopropanolamine,2-amino-2-methyl-1,3-propanediol, 3-amino-1,2-propanediol,3-dimethylamino-1,2-propanediol and tris(hydroxymethylamino)methane.

More particularly, the amino acids that can be used are of natural orsynthetic origin, in their L, D or racemic form, and comprise at leastone acid function chosen more particularly from carboxylic acid,sulfonic acid, phosphonic acid or phosphoric acid functions. The aminoacids may be in neutral or ionic form.

As amino acids that may be used in the present invention, mention may bemade in particular of aspartic acid, glutamic acid, alanine, arginine,ornithine, citrulline, asparagine, carnitine, cysteine, glutamine,glycine, histidine, lysine, isoleucine, leucine, methionine,N-phenylalanine, proline, serine, taurine, threonine, tryptophan,tyrosine and valine.

The organic amine may also be chosen from organic amines of heterocyclictype. Besides histidine that has already been mentioned in the aminoacids, mention may in particular be made of pyridine, piperidine,imidazole, triazole, tetrazole and benzimidazole.

Preferably, the basifying agent(s) present in the composition of theinvention are chosen from alkanolamines and amino acids in neutral orionic form, in particular basic amino acids. According to a particularlypreferred mode, the basifying agent(s) are chosen from monoethanolamine(MEA) and basic amino acids in neutral or ionic form.

Advantageously, the composition according to the invention has a contentof basifying agent(s) ranging from 0.01% to 30% by weight and preferablyfrom 0.1% to 20% by weight relative to the weight of the composition.

According to a first embodiment, the composition predominantly containsammonia as basifying agent.

According to another embodiment, the composition contains ammonia and atleast one other basifying agent, preferably chosen from alkanolamines.In this case, the composition comprises ammonia or a salt thereof, in anamount less than the amount of basifying agent(s) other than ammonia(expressed as NH₃). In particular, the composition contains little or noammonia. Preferably, according to this embodiment, the ammonia contentis less than or equal to 0.03% by weight (expressed as NH₃), preferablyless than or equal to 0.01% by weight, relative to the weight of thecomposition of the invention. Preferably, the composition contains noammonia.

Chemical Oxidizing Agent

The composition of the invention may comprise one or more chemicaloxidizing agents. The term “chemical oxidizing agent” means an oxidizingagent other than atmospheric oxygen. More particularly, the chemicaloxidizing agent(s) are chosen from hydrogen peroxide, urea peroxide,alkali metal bromates, peroxygenated salts, for instance persulfates orperborates, peracids and precursors thereof and alkali metal oralkaline-earth metal percarbonates.

Advantageously, this oxidizing agent is hydrogen peroxide.

The concentration of chemical oxidizing agents may range moreparticularly from 0.1% to 50% by weight, even more preferentially from0.5% to 20% by weight and better still from 1% to 15% by weight relativeto the weight of the composition.

Preferably, the composition of the invention does not contain anyperoxygenated salts.

Solvent

The composition according to the invention may also comprise one or moreorganic solvents.

Examples of organic solvents that may be mentioned include linear orbranched C₂-C₄ alkanols, such as ethanol and isopropanol; glycerol;polyols and polyol ethers, for instance 2-butoxyethanol, propyleneglycol, dipropylene glycol, propylene glycol monomethyl ether,diethylene glycol monomethyl ether and monoethyl ether, and alsoaromatic alcohols or ethers, for instance benzyl alcohol orphenoxyethanol, and mixtures thereof.

The solvent(s), if they are present, represent a content usually rangingfrom 1% to 40% by weight and preferably from 5% to 30% by weightrelative to the weight of the composition.

Other Ingredients

The composition according to the invention may also contain variousingredients conventionally used in hair dye compositions, such asanionic, cationic, nonionic, amphoteric or zwitterionic polymers ormixtures thereof; mineral thickeners, and in particular fillers such asclays or talc; organic thickeners with, in particular, anionic,cationic, nonionic and amphoteric polymeric associative thickeners;antioxidants; penetrants; sequestrants; fragrances; dispersants;film-forming agents; ceramides; preserving agents; opacifiers; anionic,cationic, amphoteric and/or nonionic surfactants.

The above ingredients are generally present in an amount, for each ofthem, of between 0.01% and 20% by weight, relative to the weight of thecomposition.

The composition of the invention may be in various forms, for instance asolution, an emulsion (milk or cream) or a gel, preferably in the formof an emulsion.

Processes of the Invention

The composition according to the invention is applied to wet or drykeratin fibres. It is left in place on the fibres for a time generallyof from 1 minute to 1 hour and preferably from 5 minutes to 30 minutes.According to a preferred embodiment, the composition applied contains atleast one basifying agent and at least one oxidizing agent.

The temperature during the dyeing process is conventionally between roomtemperature (between 15° C. and 25° C.) and 80° C. and preferablybetween room temperature and 60° C.

After the treatment, the human keratin fibres are optionally rinsed withwater, optionally washed with a shampoo and then rinsed with water,before being dried or left to dry.

According to a preferred embodiment, the composition according to theinvention is prepared by mixing at least two compositions, a firstcomposition (A) which comprises the oxidation base3-(2,5-diaminophenyl)-1-propanol, the heterocyclic base(s) and/or anacid salt or solvate thereof and a second composition (B) whichcomprises at least one chemical oxidizing agent.

In a preferred variant of this embodiment, at least one of thecompositions (A) or (B) comprises the fatty substance(s) as definedpreviously such that the fatty substance content of the compositionresulting from the mixing of compositions (A)+(B) is at least 10%,preferably greater than 25%, preferably greater than 30% by weight,relative to the weight of the composition derived from the mixing of(A)+(B).

According to one embodiment, at least one of the compositions (A) or (B)is aqueous, and preferentially both compositions (A) and (B) areaqueous.

The term “aqueous composition” means a composition comprising at least5% water. Preferably, an aqueous composition comprises more than 10% byweight of water and more advantageously still more than 20% by weight ofwater.

In one variant of the invention, at least part of the fatty substance(s)is present in a third composition which is mixed with compositions (A)and (B) under the conditions defined above. Preferably, this thirdcomposition is anhydrous.

More particularly, for the purposes of the invention, the expression“anhydrous cosmetic composition” means a cosmetic composition with awater content of less than 5% by weight, preferably less than 2% byweight and more preferably still less than 1% by weight relative to theweight of said composition. It should be noted that the water present inthe composition is more particularly “bound water”, such as water ofcrystallization in salts, or traces of water absorbed by the startingmaterials used in the preparation of the compositions according to theinvention.

The examples that follow serve to illustrate the invention without,however, being limiting in nature.

EXAMPLES Example 1

The following compositions are prepared in which the amounts areexpressed in grams of active materials.

Dye Compositions (g %)

Ingredients Composition A Composition B Sodium metabisulfite in powerform 0.45 0.45 Pure monoethanolamine 5.1 4.93 Ethylenediaminetetraaceticacid 0.2 0.2 6-Hydroxybenzomorpholine 0.161-Methyl-2-hydroxy-4-β-hydroxyethylaminobenzene 0.221-β-Hydroxyethyloxy-2,4-diaminobenzene 0.19 dihydrochloride2-Methyl-1,3-dihydroxybenzene (2-methylresorcinol) 0.3 0.05 Purified5-amino-6-chloro-o-cresol 0.2 0.032,3-Diamino-6,7-dihydro-1H,5H-pyrazolo[1,2- 1.2 A]pyrazol-1-onedimethane sulfonate 2-[(3-Aminopyrazolo[1,5-a]pyridin-2-yl)oxy]ethanol0.1 hydrochloride 3-(2,5-Diaminophenyl)propan-1-ol hydrochloride 0.20.57 4-(3-Aminopyrazolo[1,5-a]pyridin-2-yl)-1,1- 0.01dimethylpiperazin-1-ium, HCl Mineral oil (INCI name) 60 60 Perfume 0.720.72 Cationic hydroxyethylcellulose (Polyquaternium-67) 0.19 0.19marketed under the name Softcat Polymer SL-100 by Dow Chemical Deionizedwater qs 100 qs 100 Oxyethylenated stearyl alcohol (2 OE) 1.13 1.13Oxyethylenated stearyl alcohol (20 OE) 3.88 3.88 Caprylyl/caprylglucoside (alkyl (C8/C10 50/50) 2.4 2.4 polyglucoside (2) in 60%buffered aqueous solution) Oxyethylenated sorbitan monolaurate (4 OE)2.4 2.4 Vitamin C: ascorbic acid 0.25 0.25

Oxidizing Composition C (g %)

Ingredients Composition C Pentasodium pentetate 0.06 Hydrogen peroxide 6Sodium stannate 0.04 Phosphoric acid qs pH = 2.2 Tetrasodiumpyrophosphate 0.03 Mineral oil 20 Hexadimethrine chloride 0.15Polyquaternium-6 0.2 Water qs 100 Glycerol 0.5 Cetearyl alcohol 6Steareth-20 5 PEG-4 Rapeseedamide 1.2 Tocopherol 0.1

At the time of use, each of the compositions A and B is mixed with onetime its own weight of oxidizing composition C.

The mixtures thus obtained are applied to natural hair containing 90%white hairs.

After a leave-on time of 35 minutes at room temperature, the hair isrinsed and washed with a standard shampoo.

After drying, an attractive Coppery Red Dark Blonde shade of hair isobtained with formula A and a Dark natural shade of hair is obtainedwith formula B.

Example 3

The following compositions have been prepared in which the amounts areexpressed in grams of active materials.

C (inv) C′ (comp) Ethanolamine 4 4 Sodium LAURYL ETHER SULFATE (2.2 EO)in 2.5 2.5 an aqueous solution (70%) HYDROXYETHYL CELLULOSE (PM: 2.5 2.51.300.000) ANTI-OXYDANT 0.5 0.5 1-METHYL-2-HYDROXY-4-BETA- 0.5 0.5HYDROXYETHYLAMINOBENZENE 1-METHYL-2-HYDROXY-4-AMINO-BENZENE 0.5 0.51,3-DIHYDROXYBENZENE (RESORCINOL) 0.2 0.2 2,3-DIAMINO-6,7-DIHYDRO-1H,5H-4.04.10⁻³ mol 4.04.10⁻³ mol PYRAZOLO[1,2-A]PYRAZOL-1-ONEDIMETHANESULFONATE 3-(2,5-DIAMINOPHENYL)PROPAN-1-OL- 3.43 × 10⁻³ mol —HYDROCHLORIDE (2,5-diaminophenyl)ethanol — 3.43 × 10⁻³ mol SEQUESTRANT 22 Coco-betaine 3 ma 3 ma REDUCTEUR (Sodium meta bisulphite) 0.5 0.5Mineral Oil 60 60 PEG-40 hydrogenated castor oil 1 1 water Qsp 100 Qsp100

Oxyidizing composition Ox2 Hydrogen peroxide in an aqueous solution 50%6 ETIDRONIC Acid, TETRA sodium salt in an aqueous 0.2 solution (30%)Tetra sodium PYROPHOSPHATE, 10 H₂O 0.04 SODIUM Salycilate 0.035 DIMETHYLDIALLYL AMMONIUM CHLORIDE/ 0.74 ACRYLIC ACID COPOLYMERE (80/20) IN ANAQUEOUS SOLUTION (Merquat 280) GLYCEROL 4 CAPRYLYL/CAPRYL GLUCOSIDE(ALKYL (C8/ 3 C10 50/50) POLYGLUCOSIDE IN AN AQUEOUS SOLUTION (60%)WATER qsp 100

At the time of use, each composition C′ and C is mixed with theoxidizing composition Ox2 at a weight ratio of 1/1.

The resulting mixture are each applied on natural locks with 90% ofwhite hair (BN) and on permed hair locks with 90% of white hair (BP inan amount of 10 g of the resulting mixture per 1 g of hair, and left for35 minutes at room temperature (25° C.).

Then the hair was rinsed with water, washed with the “Pro Classicsconcentrated” shampoo (L'Oreal Professionnel), diluted at 10%, anddried.

Selectivity Evaluation

The color of the hair was determined using the CIE L*a*b* system with aMinolta CM2006D spectrophotometer (illuminant D65, angle 10°, specularcomponent included) in the CIELab system.

According to this system, L* indicates the lightness of the color of thehair.

The chromaticity coordinates are expressed by the parameters a* and b*,a* indicating the axis of red/green shades and b* the axis ofyellow/blue shades.

The selectivity of the dyeing is measured by calculating the variationof ΔE according to the formula:

ΔE=√{square root over ((L*−L _(o))²+(a*−a _(o)*)²+(b*−b _(o)*)²)}

In which L, a* and b* represent the values measured on permed hair andL0*, a0* and b0* represent the values measured on natural hair.

The selectivity is represented by the difference of color between thecolored natural hair representative of the hair roots and permed hairrepresentative of hair tips: the more is the ΔE value, the more thedifference of color between natural and permed hair is important. Alesser selectivity is representative of an homogeneity of the colorationbetween the roots and the tips along the lock of hair.

The following results are obtained:

Hair type L* a* b* ΔE C + O2 (inv) BN 26.9 15.2 10.6 9.3 BP 20.9 10.65.0 C′ + O2 BN 29.6 18.4 13.7 12 (comp) BP 21.8 12.8 6.5

The resulting composition C+O2 according to the invention exhibits a ΔEvalue lesser than the one obtained with the C′+O2 comparative mixture.The hair coloration resulting from the use of C+O2 provides on hair animproved homogeny coloration along the hair fibers.

1. Composition comprising: a) at least one oxidation base3-(2,5-diaminophenyl)-1-propanol and/or acid salts thereof and/orsolvates thereof such as hydrates; b) at least one heterocyclicoxidation base chosen from oxidation bases of pyridine, pyrimidine typeand pyrazolone of formula (I), and the addition salts thereof orsolvates thereof

in which R₁ represents an amino group, a C₁ to C₄ alkyl group optionallysubstituted with one or more hydroxyl or amino groups, or a C₁ to C₄alkoxy group optionally substituted with one or more hydroxyl or aminogroups, c) at least one coupler; d) optionally at least one fattysubstance; e) optionally at least one basifying agent; and f) optionallyat least one chemical oxidizing agent.
 2. Composition according to thepreceding claim, comprising at least one fatty substance, preferablychosen from C₆-C₁₆ hydrocarbons, hydrocarbons containing more than 16carbon atoms, non-silicone oils of animal origin, plant oils oftriglyceride type, synthetic triglycerides, fluoro oils, fatty alcohols,esters of fatty acids and/or of fatty alcohols other than triglyceridesand plant waxes, non-silicone waxes and silicones.
 3. Compositionaccording to any one of the preceding claims, characterized in that thefatty substance(s) are liquid at room temperature and at atmosphericpressure, and are preferably non-silicone-based.
 4. Compositionaccording to any one of the preceding claims, characterized in that thefatty substances are chosen from C₆-C₁₆ hydrocarbons, hydrocarbonscontaining more than 16 carbon atoms, triglycerides, fatty alcohols,esters of fatty acids and/or of fatty alcohols other than triglycerides,or mixtures thereof, and preferably from liquid petroleum jelly,polydecenes, liquid fatty alcohols, liquid esters of fatty acids and/orof fatty alcohols, or mixtures thereof.
 5. Composition according to anyone of the preceding claims, characterized in that the concentration offatty substances represents at least 10% by weight relative to the totalweight of the composition, preferably ranges from 15% to 80% by weight,preferentially from 25% to 75% by weight, in particular from 30% to 70%by weight and advantageously from 30% to 60% by weight relative to thetotal weight of the composition.
 6. Composition according to any one ofthe preceding claims, in which the coupler is chosen frommeta-phenylenediamines, meta-aminophenols, meta-diphenols,naphthalene-based couplers and heterocyclic couplers, and the additionsalts thereof.
 7. Composition according to any one of claims 1 to 5, inwhich the heterocyclic base(s) is an oxidation base of formula (I)chosen from 2,3-diamino-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-one,an addition salt thereof or a solvate thereof.
 8. Composition accordingto any one of claims 1 to 6, in which the heterocyclic oxidation base(s)are chosen from the compounds of formula (II) or (III), the additionsalts thereof and solvates thereof:

in which R₂ represents an amino group, a C₁ to C₄ alkyl group,optionally substituted with one or more hydroxyl or amino groups, a C₁to C₄ alkoxy group, optionally substituted with one or more hydroxyl oramino groups; and Z, represents a covalent bond, a radical—NR′₆(CH₂)_(q)— or a radical —O(CH₂)_(p)— with R′₆ representing ahydrogen atom, a C₁-C₆ alkyl radical optionally substituted with one ormore hydroxyl groups, p denoting an integer ranging from 0 to 6, qdenoting an integer ranging from 0 to 6 and R′₁ is a cationic radical;the radicals R′₃, R′₄ and R′₅ independently represent a hydrogen atom ora C₁-C₄ alkyl radical which may be substituted, R′₄ and R′₅ may togetherform a partially saturated or unsaturated 5- or 8-membered ring. 9.Composition according to any one of claims 1 to 8, in which theheterocyclic oxidation base(s) is an oxidation base of formula (II) inwhich R₂ represents a C₁ to C₄ alkoxy group optionally substituted withone or more hydroxyl groups, and preferentially represents ahydroxyethoxy group.
 10. Composition according to any one of claims 1 to8, in which the heterocyclic oxidation base is an oxidation base offormula (II) chosen from2-[(3-aminopyrazolo[1,5-a]pyrid-2-yl)oxy]ethanol, an addition saltthereof or a solvate thereof.
 11. Composition according to any one ofclaims 1 to 8, in which the heterocyclic oxidation base is an oxidationbase of formula (III) chosen from4-(3-aminopyrazolo[1,5-a]pyridin-2-yl)-1,1-dimethylpiperazin-1-ium, anaddition salt thereof or a solvate thereof.
 12. Composition according toany one of the preceding claims, in which the oxidation base(s) chosenfrom 3-(2,5-diaminophenyl)-1-propanol and/or the acid salts or solvatesthereof, and the heterocyclic oxidation base(s) and the acid salts orsolvates thereof such as hydrates, are in an amount ranging from 0.0001%to 20% by weight relative to the total weight of the composition,preferably from 0.005% to 10% by weight, in particular from 0.01% to 10%by weight relative to the total weight of the composition. 13.Composition according to any one of the preceding claims, whichcomprises at least one basifying agent chosen from ammonia, alkali metalcarbonates or bicarbonates, sodium hydroxide or potassium hydroxide,organic amines chosen from alkanolamines, oxyethylenated and/oroxypropylenated ethylenediamines, amino acids and the compounds offormula (T), or mixtures thereof:

in which formula (T) W is a divalent C₁-C₆ alkylene radical optionallysubstituted with one or more hydroxyl groups or a C₁-C₆ alkyl radical,and/or optionally interrupted with one or more heteroatoms such as O, orNR_(u); R_(x), R_(y), R_(z), R_(t) and R_(u), which may be identical ordifferent, represent a hydrogen atom or a C₁-C₆ alkyl, C₁-C₆hydroxyalkyl or C₁-C₆ aminoalkyl radical.
 14. Composition according toany one of the preceding claims, in which the basifying agent is chosenfrom ammonia or alkanolamines, preferably monoethanolamine, and neutralor ionic amino acids.
 15. Composition according to any one of thepreceding claims, which comprises a chemical oxidizing agent, preferablyhydrogen peroxide.
 16. Process for dyeing keratin fibres, in particularthe hair, comprising the application to the keratin fibres of thecomposition as defined according to any one of the preceding claims. 17.Process according to the preceding claim, in which the composition asdescribed according to any one of claims 1 to 15 is obtained by mixingat least two compositions, a first composition (A) which comprises theoxidation base 3-(2,5-diaminophenyl)-1-propanol and/or acid saltsthereof or solvates thereof and the heterocyclic oxidation base(s) asdefined above and/or an acid salt thereof or solvate thereof and asecond composition (B) which comprises at least one chemical oxidizingagent.
 18. Process according to claim 17, in which at least one of thecompositions (A) or (B) comprises one or more fatty substances asdefined previously such that the content of fatty substance in thecomposition resulting from the mixing of compositions (A) and (B) is atleast 10%, preferably greater than 25%, preferably greater than 30% byweight, relative to the weight of the composition derived from themixing of (A) and (B).
 19. Process according to claim 17, in which thecomposition applied to the fibres is obtained from the composition (A),from the composition (B) and from a third composition at least partlycomprising the fatty substance(s), this third composition preferablybeing anhydrous.
 20. Multi-compartment device comprising a firstcompartment containing composition (A) which comprises the oxidationbase 3-(2,5-diaminophenyl)-1-propanol and/or acid salts thereof orsolvates thereof, and the heterocyclic oxidation base(s) as definedabove and/or an acid salt thereof or solvate thereof and a secondcompartment containing composition (B) which comprises at least onechemical oxidizing agent, preferably at least one of the compositions(A) or (B) comprises the fatty substance(s) as defined previously suchthat the fatty substance content of the composition resulting from themixing of compositions (A) and (B) is at least 10%, preferably greaterthan 25%, preferably greater than 30% by weight, relative to the weightof the composition derived from the mixing of (A) and (B).